Resinous reaction product of polymerized fatty acid ester, rosin, and trialkanolamine



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'nfislfious; aEAc'rioN PRODUCT Phimm f MERIZED FATTY ACID ESTER, ROSINp-AND i Charles F. Brown, Naugatucir, Conn., assignorto, .r-United States Rubber Company. New, York 7 4 i i,

- 3N. Y.,,a corporation of New Jersey 1 6 Draw n Application-October 22, 1943, r

I I v I "Serial No. 507,295 v 1w 9 Claims. (01.,260-23) a I I; Y I .I 1 I I J v This invention relates to improvements-in resin the' glycol seems to actas-a-plasticizer and does compositions.

1 not materially change the basicresirr fo'rr'riedu 'ln An object of the invention is toprepare a new, any case, the reactions arecom'plex, resulting {in adhesive, moisture-resistant composition thatis "a heterogeneous product having newand novel flexible and stable over a'wide temperature range 5 characteristics. 1 3 and which is resistant to deterioration by ageing Polyesters suitable for practice/ of the-" pres'ent and/or chemical agents. A further object is to, invention aresold in-the trade'underthe 'names provide such a product as willimpart these char- ;Norep0l, Agripol, and the like. These'polyesters acteristics to a marked degree tomixtures into may or may not be in a gel form when introduced which the composition may be incorporated. into the reaction mixture. .The dimerized; acid Other objects will be apparent fromthe hereinand glycol may be added in the proper proportion after detailed description. a i separately-to the reaction mixture,.:as-illustrated- Broadly, the invention involves the, production in Examples III and 2-"! below. {The proportion of such a useful'resinous composition from'heatof the reactants may be varied over a wide range ing a: mix containing an amine, .isuch as .15 and they may beadmi'xed with other materials triethanolaminea polyester which is a reaction before, during or. after the reaction, which other product obtained by reacting a dimerized higher materials add to the strength of the final corni'atty acid with a glycol such as ethylene. glycol," position without materially changing the g- .and a resin acid or acid resin which contains such erty of the basic resin material. For example, a

an acid, such as, ordinary", rosin, whichcontains go polyvinyl acetal resin may be additionally added. such as abietic acid and its isomers, and pirnaric Generally, useful proportions, by -weight, "are acid, or homologs thereof. The amine may =exemplifled by the following:

r i Parts either a monoor d1 substituted alkanolamine,

e. g., monoethanolamine and/or diethanolam-ine, 3 1;, I I 5400 although these are less preferred than. the trizl th m m 25-1100 substituted alkanolamina. Generally,-the reac- Polyester :50- 200 tion range is between about 180 C. and 309 C... Polyvinyl aoetal resin 01,25 The time may range from aboutl.5..to about 15 Preferred proportions, by weight, as illustrated For o of brevity, t h. o n by the examples below, comprise about equal parts :ester as used broadly herein, except where otherof the rosin" (or its equivalent 0f abietic acid.)

wise ljmited means a reaction product obtained and the ethanolamine; together about by reacting a glycol withia long chain m n 85 to about 100 parts of thepolyester based on acid of animal or vegetableorigina A "polyester each 100 parts of the rosin. r

Ito givevarious products vdiffering from the origi- 45 to b u 18 h F i s' f die s'i of ethylene glycol refers to such an ester where- 1 e following examples, in W i hv Parts are in ethylene glycol is the glycol which is usedi By a y weigh are n in i r n of the inv dimerization is meantthe combination of. two tion: v

molecules of the acids toproduce onereactive V Example -I entity and not an individual molecule. y W

The reactions taking p1ace,between the com- 40 m I l i -R.os1n ,100 ponents present are varied and complex. 1 The H Triethanolamine polyester when added as such probablybreaks, 1 i

. Polyester I i 100 down into its several reacting groups, which i groups or bodies react with votherbodies present The and the. m r mixed nd e ig nal reactants. The dimerized acid and glycol, hmgenebus Stillman-r ll h 1 9M355 when added separately either provide such ref added and the IeaCtiOn active groups, or may react to give pm t zether in a suitable container at ZOO-230 C. for

which in turn may give up reactive bodies as m 9 I- incipient, gelling postulated. The dimerized acid and glycol, when 0 takes. p fi At the ll,9 8 l he added separately, should, be added to a weight mixture is dumped from a s i-rq se e equivalentto the weight of, the polyester. For i allowed t 0 11 The P d t .1 a d rk. .v y

' example, 87.5 parts of dimerized acids of soybean sticky" si e gel'lilFe resin that nsq oil, and 12.5 parts of ethylene glycol, are equiv- 1 Y .7 f l 1 This. 01 ester and that oi. Exam les II and-Vie a coma e to v1 parts tt r n s polyesterat bimlii'tion przpgred frlom 1 tiiiilneriizgdi 1.1 am In some cases, an excess of the. g ycol may be used 91mm B8 I a r withthl ,11 m. dt H beyond that entering into combination. As such, shout rz u fer ce if egh fiene g ly cgifg;

a 3 in all or the common solvents, except the benzenoidand chlorinated hydrocarbons.

Example I! The reaction product may be further modifled by the incorporation of other resins. These resins serve to add strength to the composition and do not materially change the properties of the basic resins. A preferred mixture is:

'Parts Rosin 100 Triethanolamine 100 Polyester 85 Polyvinyl butyral resin The reaction mixture is heated as in Example I. The resin produced has characteristics substantially identical with that cited in Example I except that the composition is stifier and stronger. Analysis shows the product from Example II to have a saponification number of approximately 60, an iodine number of approximately 100,;and'

an acid number of approximately 5.

The ageing characteristics of the gel-like resin or end product produced in the present invention, is very good, the characteristics remaining the same over an extended period of time} when stored at room conditions. The material is flexible at lower than 40 C. and is still a semisolid at the thermal decomposition point of approximately 360-375" C.

Example II! It is not always necessary that the polyester be added assuch. The ingredients may be added separately. The following example is illustrative:

Parts Rosin 100 Triethanolamine 100 Dimerized acid 2 87.25 Ethylene glycol 12.75

The reactants are heated'to'gether as in Example I and the resin produced has characteristics equivalent to that of Example I.

1 Example IV A resin corresponding to that produced in Ex- .ample II is obtainedfrom:

x g Parts Rosin 100 Triethanolamine 100 Dimerized acids 74.4 Ethylene glycol 10.6

Fr'olyvinyl butyi'al resin 15 n: The reactants are heated together as in Example and the products obtained are substantially ividfilltlCQJ in characteristics with those irom ExampleII.- g Thereaction need not be :carried to completion -;to produce newcanduseful products. A.-useful adhesive andsticky composition oimatter is'xobtained as follows I Example v Triethanolamine .-"1-00 P'olyes'ter 100 This uI tsa-iand that of Examples 115m v in mm- 1 nation prepai'ed from a dimerized a'cid derived from s'soy bean oil, said dimerized acid-being reacted with efhylcne glycol and the reaction product containing about 12 1:; percent ethylene glycol *Ccrrcsponds to a higher fatty those from soy bean oil.

acid or acids such as first six hours 01' heat. When the reaction has,

reached the point at which the resin mix does not become opalescent when rubbed with water, and is still fluid at 200 C., the heat is discontinued. This product is in a lower state of polymerization than that of the resin prepared in Example I. The composition is soluble in a wider range of materials than if the reaction is carried to completion. This solubility variation is probably due to the difierence in polymerization. These solubility characteristics make it possible to combine the product with various materials to obtain a variety of adhesive mixtures, hot melt, and coating compositions.

Compositions obtained as from Examples 1 and II are compatible with various materials including natural resins or pitches, such as. rosin or asphalt,,and synthetic resins, such as polyvinyl acetates, polyvinyl acetals, certain methacrylate resins, and other synthetic resins that are generally soluble in, and compatiblewith benzenoid hydrocarbons. When incorporated with these types of materials, the resulting composition can bemade adhesive, pliable, and otherwise modifled, the adhesive and flexible qualities depending on the amount and type of resin from the present invention that is incorporated in the mix.

Solutions; and aqueous dispersions of the present -'composition are excellent adhesives. These adhesives may be used for combining fabrics, wood, and like fibrous materials; also, for

adhesion to regenerated cellulose, cellulose. es-

ters, glass, metal, and generally most types of f surfaces. Such adhesives are permanently tacky, thermoplastic, and are particularly water-resistant. a

While I have shown and described various embodiments of the invention, it is to be understood that the invention is susceptible to those modifications which appear within the spirit of the invention and the scope of the appended claims.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. A resinous composition which is the heat reactionproduct, at a temperature in the range oi between about 180 C. and 300 C., of a-mix containing a rosin acid, a tri-alkanolamine, and a. polyester of ethylene glycol and-a dimerized soy bean oil fatty acid. I

2. A resinous composition which is the heat reaction product, at a temperature in the range of between about 180 C. and 300 C., of a mix containing a rosin acid, a tri-alkanolamine,

ethylene glycol, and a dimerized higher fatty acid derived from soy bean oil.

3. A resinous composition which is the heat I reaction product, at a temperature in the range o5] I p 4 A resinous composition which is the heat ,reaction product, at a temperature in the range of between about C. and 300 C., of a mix containing abietic acid, triethanolamine, and a polyester of ethylene glycol and a. dimerized soy bean oil fatty acid.

of between about 180 C. andabout 300 C., of a mix containing rosin, triethanolaminaa polyester of ethylene glycoland a dimerized higher fatty acid derived from soy bean oil.

' 5. A resinous composition which is, the heat f reaction product, at a, temperature in the range of between about 180C. and about 300 C., of a mix containing rosin, triethanolamine, a polyester of ethylene glycol and a dimerized soy bean oil fatty acid, and a polyvinyl acetal resin.

6. A resinous composition which is the heat reaction product, at a temperature in the range of between'about 180 C. and about 300 C., of a mix containing rosin, triethanolamine, ethylene glycol, and a. dimerized higher fatty acid derived from soy bean oil.

'7. A resinous composition which is the heat reaction product, at a temperature in the range of between about 180 C. and about 300 C., of a mix containing rosin, triethanolamine, ethylene glycol, a dimerized soy bean oil fatty acid, and a polyvinyl acetal resin. I

8. A resinous composition which is the heat reaction product, at a temperature in the range of between about 180 C. and 300 (2., of a mix containing a rosin acid, a trialkanolamine, and

' a, polyester of ethylene glycol and a dimerized fatty acid selected from the dimeriiable fatty acids whose glycerides occur in animal and vegetable oils.

9. A resinous composition which is the heat 3 reaction product, at a temperature in the range from. about 180 C. to about 300 C., of a 'mix containing rosin, a trialkanolamine, ethylene glycol and a dimerized soy bean oil fatty acid.

CHARLES F. BROWN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,308,530 McManus Jan. 19, 1943 2,312,879 Christ Mar. 2, 1943 FOREIGN PATENTS,

Number Country Date 378,596 British Aug. 12, 1932 428,864 British May 15, 1935' OTHER REFERENCES Bradley et al. Ind. & Eng. Chem., vol. 33, No. 1, Jan. 1941, pages 86-89. (Copy in Scie. Libr.) 

